Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
  • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
  • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
  • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
  • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
  • C07D239/47—One nitrogen atom and one oxygen or sulfur atom, e.g. cytosine
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
  • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
  • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
  • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
  • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
  • C07D239/48—Two nitrogen atoms
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
  • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
  • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
  • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
  • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
  • C07D239/32—One oxygen, sulfur or nitrogen atom
  • C07D239/38—One sulfur atom

Definitions

• the present invention relates to new 2,4-diamino-6-halogen-5-alkylthio-pyrimidines, processes and new intermediates for their preparation and their use as crop protection agents, in particular as herbicides and fungicides.
• 2,4-diamino-6-chloro-5-alkylthio-pyrimidines can be used as herbicides (cf. EP-A-0 000 681).
• 2,4-diamino-6-chloro-5-methylthio-pyrimidine can be used as a selective herbicide in cereals, corn, rice and sorghum in the pre- and post-emergence process; however, its effect at low application rates is unsatisfactory for various harmful plants.
• the previously known group of compounds is also said to have a certain fungicidal activity (cf. FR-A-2 119 234), but the activity has proven to be insufficient in a number of fungal diseases under practical conditions. In particular, nothing is known about an action of these compounds against Pyricularia oryzae on rice.
• the new pyrimidine derivatives of the formula (I) according to the invention are structurally distinguished from the previously known pyrimidines in particular in that the 2-amino group is a straight-chain or branched alkoxyalkylamino group.
• the active compounds of the formula (I) according to the invention are significantly more effective than the previously known pyrimidine derivatives.
• the active compounds according to the invention are more effective against Panicum, Chenopodium, Poa and Setaria than the previously known 2,4-diamino-6-chloro-5-methylthiopyrimidine.
• the pyrimidine derivatives according to the invention also have strong fungicidal properties at low concentrations which are not suitable for herbicide use.
• the trihalopyrimidines used as starting materials are generally defined by the formula (II).
• R 1 and X preferably or particularly preferably represent those radicals which have already been mentioned as preferred or particularly preferred for these substituents in the description of the substances of the formula (I) according to the invention.
• the amines which are also used as starting materials are generally defined by the formulas (III) and (V).
• R 2 , R 3 , R 4 , R 5 and Z preferably or particularly preferably represent those radicals which have already been mentioned as preferred or particularly preferred for these substituents in the description of the substances of the formula (I) according to the invention .
• the amines of the formulas (III) and (V) are known or can be prepared by known processes in a manner analogous to the known compounds (cf., for example, Houben-Weyl, Methods of Organic Chemistry, Volume XI / 1, p. 548, p 561 ff., 4th edition 1957).
• Organic solvents and water are suitable as diluents for the process according to the invention.
• Preferred organic solvents are hydrocarbons such as toluene, aliphatic ketones such as acetone, methyl ethyl ketone and diethyl ketone, cycloaliphatic ethers such as tetrahydrofuran or dioxane. Mixtures of various organic solvents and mixtures of water-miscible organic solvents with water are also suitable as diluents.
• alkaline earth and alkali metal hydroxides such as calcium, sodium or potassium hydroxide, ammonia and tertiary aliphatic amines such as e.g. Triethylamine, but also amine starting product (III) or (V) used in excess.
• the reaction temperatures can be varied within a wide range in the process according to the invention.
• the first process stage is generally carried out at temperatures from -30 to + 150 ° C, preferably from -20 to + 30 ° C; the second stage of the process is generally carried out at 80 to 150 ° C., preferably at 90 to 130 ° C.
• the reaction is carried out in the pressure range from 1 to about 10 bar.
• amine of the formula (III) or (V) and 1 to 1.2 mol of acid binder are generally employed in 1 mol of trihalopyrimidine of the formula (II) in the first stage , the amine (III) or (V) can be used as the acid binder. It is preferred to use stoichiometric molar ratios. The same applies to the second stage of the process.
• the isomer mixtures obtained in both process stages can be easily prepared using known methods be separated, in particular by recrystallization (see, for example, FR-A 2 119 231), so that the desired isomers can be isolated in a sufficiently pure form.
• the active compounds according to the invention can be used as defoliants, desiccants, haulm killers and in particular as weed killers. Weeds in the broadest sense are understood to mean all plants that grow up in places where they are undesirable. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
• the compounds are suitable for total weed control, e.g. on industrial and track systems and on paths and squares with and without tree cover.
• the compounds for weed control in permanent crops e.g. Forestry, ornamental trees, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hop plants and for selective weed control in annual crops.
• the active compounds according to the invention can - especially in the post-emergence process - for selective weed control in monocotyledon crops, e.g. in corn and cereals.
• the new active ingredients are significantly more effective than the previously known compound 2,4-diamino-6-chloro-5-methylthiopyrimidine.
• the active compounds according to the invention also have a strong microbicidal action and can be used practically to combat unwanted microorganisms.
• the active ingredients are suitable for use as pesticides.
• Fungicidal agents in crop protection are used to control Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.
• the active compounds according to the invention can be used particularly successfully as plant protection agents for systemic control of rice diseases, such as Pyricularia oryzae.
• the active compounds can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, and ULV formulations.
• formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents and / or solids Carriers, where appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents.
• organic solvents can also be used as auxiliary solvents.
• auxiliary solvents e.g. organic solvents
• aromatics such as xylene, toluene, or alkylnaphthalenes
• chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride
• aliphatic hydrocarbons such as cyclohexane or paraffins, e.g.
• Petroleum fractions mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
• alcohols such as butanol or glycol and their ethers and esters
• ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone
• strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
• adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers, such as gunmiarabicum, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used.
• Other additives can be mineral and vegetable oils.
• Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
• the formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
• the active compounds according to the invention can also be used as mixtures with known herbicides for weed control, ready-to-use formulations or tank mixes being possible.
• ureas e.g. methabenzthiazuron
• Diphenyl ether e.g. acetanilides
• acetanilides e.g. alachlor, metolachlor
• Phenoxyalkane carboxylic acids e.g. 2,4-D, 2,4-DP, MCPA, MCPP and their derivatives
• Aryloxy and hetaryloxy phenoxypropionic acids e.g. 2- [4- (3,5-dichloro-2-pyridyloxy) phenoxy] propionic acid (trimethylsilylmethyl) ester; 2-L4- (3,5-dichloro-2-pyridyloxy ) -phenoxy7-propionic acid (2,2-diethoxy) ethyl ester; 2- / 4- (3,5-dichloro-2-pyridyloxy) phenoxy] propionic acid (2-benzyloxy) ethyl ester); Triazines (e.g.
• Triazinones e.g. metribuzin and 4-amino-6-tert-butyl-3-ethylthio-1,2,4-triazin-5 (4H) -one
• Triazinediones e.g. ametridione
• a mixture with other known active compounds such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents which improve soil structure, is also possible.
• the active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the usual way, e.g. by pouring, spraying, spraying, scattering, dipping, atomizing, vaporizing, injecting, slurrying, spreading, dusting, dry pickling, wet pickling, wet pickling, slurry pickling or incrusting.
• the active compounds according to the invention can be applied both before and after emergence of the plants. It is preferably used after the plants have emerged, that is to say in the post-emergence process. They can also be worked into the soil before sowing.
• the amount of active ingredient used can fluctuate in larger areas. It essentially depends on the type of effect desired. In general, the application rates for herbicide applications are between 0.01 and 10 kg of active ingredient per ha, preferably between 0.05 and 5 kg per ha.
• active compound 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.
• active ingredient concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02% by weight, are required at the site of action.
• active compound 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
• Test plants which have a height of 5-15 cm are sprayed with the active substance preparation in such a way that the desired amounts of active substance are applied per unit area.
• the concentration of the spray liquor is chosen so that the desired amounts of active compound are applied in 2000 l of water / ha.
• the degree of damage to the plants is rated in% damage compared to the development of the untreated control.
• active compound 1 part by weight of active compound is mixed with the stated amount of solvent and the concentrate is diluted to the desired concentration with water and the stated amount of emulsifier.
• the disease infestation is evaluated 4 days after the inoculation.
• active compound 1 part by weight of active compound is mixed with the stated amount of solvent and the concentrate is diluted to the desired concentration with water and the stated amount of emulsifier.
• the disease infestation is evaluated 4 days after the inoculation.

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• Organic Chemistry (AREA)
• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Health & Medical Sciences (AREA)
• Environmental Sciences (AREA)
• Engineering & Computer Science (AREA)
• Dentistry (AREA)
• General Health & Medical Sciences (AREA)
• Wood Science & Technology (AREA)
• Zoology (AREA)
• Plant Pathology (AREA)
• Pest Control & Pesticides (AREA)
• Agronomy & Crop Science (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Plural Heterocyclic Compounds (AREA)
• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
• Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Applications Claiming Priority (2)

Publications (2)

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Family Applications (1)

Country Status (11)

Families Citing this family (3)

Family Cites Families (6)

• 1984
  • 1984-05-10 DE DE19843417264 patent/DE3417264A1/de not_active Withdrawn
• 1985
  • 1985-04-27 EP EP85105168A patent/EP0160908A3/fr not_active Withdrawn
  • 1985-05-03 US US06/730,393 patent/US4614532A/en not_active Expired - Fee Related
  • 1985-05-06 AU AU42007/85A patent/AU4200785A/en not_active Abandoned
  • 1985-05-07 IL IL75109A patent/IL75109A0/xx unknown
  • 1985-05-08 JP JP60096181A patent/JPS60239471A/ja active Pending
  • 1985-05-09 BR BR8502197A patent/BR8502197A/pt unknown
  • 1985-05-09 ZA ZA853510A patent/ZA853510B/xx unknown
  • 1985-05-09 KR KR1019850003159A patent/KR850008163A/ko not_active Withdrawn
  • 1985-05-09 DK DK207085A patent/DK207085A/da unknown
  • 1985-05-10 HU HU851783A patent/HUT39432A/hu unknown
• 1986
  • 1986-01-08 US US06/816,936 patent/US4640923A/en not_active Expired - Fee Related

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